Process for converting cyannaphthalene-sulphonic acids



Patented May 8, 1928.

UNITED STATES PATENT OFFICE.

RICHARD HEBZ AND FRITZ SCHULTE, F FRANKFORT-ON-THE-MAIN. AND WERNERZERWECK, OF FECHENHEIM, NEAR FBANKFORT-ON-THE-MAIN, GERMANY, A8- SIGNORSTO GBASSELLI DYESTUFF CORPORATION, OF NEW YORK, N. Y., A COB- PORATIONOF DELAWARE.

PROCESS FOR CONVERTING CYANNAPHTHALENE-SULPHONIC ACIDS.

Ho Drawing. Original application filed February 24, 1927, Serial No.170.732, and in Germany May 17, 1926. Divided and this application filedNovember 10, 1927. Serial No. 232,468.

This application is a division of our application Serial No. 170,732,filed February 24th, 1927.

We have found, that if cyannaphthalenesulphonic acids, containing atleast one sulphonic group in ortho-or para-position t0 the cyanic group,are treated with an alkaline acting agent at elevated temperatures, thissulphonic group, standing in ortho or para position to the cyanic group,is easily exchanged to other inonovalent radicles.

The products of conversion thus obtained correspond to the generalformula:

in which formula the group OY stands in ortho or para position to thegroup Z, the Xs mean hydrogen atoms, of which one or more may bereplaced by a monovalent substituent, Y means hydrogen or an alkylresidue, Z the groups CN, CONH and COOH.

The general formula shows the range of substances, obtained according tothe conditions applied. By acting with milder acting alkaline agents,the cyangroup of the employed cyannaphthalenesulphonic acids remainsunattached and hydroxy-cyannaphthalene-compounds are formedcorresponding to the above formula, Y being hydrogen and Z being CN, byacting with stronger alkaline acting agents the cyangroup 1S saponifiedto the carboxyamido (Z=CONH in this case) or to the carboxy-group (ZCOOH in this case) whereas the sulphonic group is exchanged by hydroxyl(OH) when the applied alkaline acting agent is an aqueous causticalkali, or by an alkoxy-group, generally when applying caustic alkalisin presence of an alcohol. This latter reaction by which an alkoxygroupis introduced in the molecule, 18 a particularly remarkable one withoutany analogy in the naphthalene series. In this manner especiallyalkoxynaphthalenccar boxyamids corresponding to the above formula, Zbeing CONH and Y being an alkylresidue, and hydroxyand alkoxynaphthoicacids are obtained corresponding to the above formula, Z being COOH andY being hydrogen or an alkylresidue.

Under the term alkaline acting agents we understand caustic alkalies inpresence of water or of an alcohol, acting either at ordinary pressureor in a closed vessel at elevated pressure. Under milder actin alkalineagents the following have been t ound especially suitable: basicalkaline salts such as sodium formiutc, acetate, borate, phosphate. Suchagents, the caustic alkalies as well as the milder acting agents may beused advantageously in presence of inorganic or organic diluents inorder to keep the mass homogeneous and easily liquid, such as parafiine,naphthalenue, tertiary aromatic bases as dimethylaniline orN-alkyl-carbazol, higher fatty acids. glycerine or low melting sa ts.

The aforesaid reactions take place at remarkable low temperatures,namely at about 80 250, whereas Boyle and Shedler and Butler and Royle(see Journ. of Chem. Soc. London, vol. 123, pa es 1641, 1649) must applytemperatures a ove 260 to 300 for exchanging the sulphonie group by thehydroxylgroup in the corresponding carboxynaphthalene-sulphonic acids.

The starting materials for these reactions, namely the orthoandpara-cyannaphthalcncsulphonic acids and their nuclear substitutionproducts, particularly those, containing a halogen or a furthersulphonic group in the nucleus, are obtainable by diazotizing thecorresponding aminonaphthalenesulphonic acids and treating thediazocompounds, thus obtained, with cuprous cyanide, according toSandineyers reaction.

All products of conversion, derived therefrom, are importantintermediates for the production of dyestuffs and pharmaceuticalproducts.

In order to further illustrate our invention the following examples aregiven.

Ewample I 40 parts of caustic potash and 40 parts of mcthylic alcoholare heated for some time at about 110. At this temperature 15 parts ofthe sodium salt of l-cyannaphthalene-Q- sulphonic acid (obtained fromthe l-amino- Q-naphthalenesulphonic acid, see Liebigs Annalen vol. 388,page 7) are added while stirring. The temperature of the mass is slowlyincreased to about 130440 and the mass is kept at this temperature for ashort time, until a test. when acidified shows that the formation of acompound, insoluble in cold water and in dilute solutions of alkali'arbonates, but soluble in ether, is finished Then the mass poured onice, the precipitate thus formed is filtered and washed with water.\Vhen riarrystallized from water or benzene the2-111ethoxy-naphtlialene-l-carboxyamide of the. probable formula:

OCH:

thus obtained forms long colorless needles, melting at 189. as describedin literature. It has been formerly prepared by Guttermann (cf. Liebig'sAnualen. vol. 244. page in a complicated manner. unlit for technicalpurposes, by reactingwith ureachloride and aluminium-chloride onB-naphtholether.

\Vhen using caustic potash in presence of ethylic or butylie alcohol inthis process the corresponding ethoxyand butyloxy-compounds areobtained.

Trample F3.

40 parts of caustic potash and 25 parts of methylie alcohol are heatedfor MJJUP time at about so". At this temperature lo parts of the sodiumsalt of 2-(Tfft1llll2ll7hllltlltllQ-lsulphonic acid are added. Thetemperature of the mass is increased to about 100-120 and the mass iskept for a. short time at this temperature, until a test as described inthe foregoing, example shows the formation of a. compound insoluble indilute solutions of alkali carbonates. Then it is cooled down anddiluted with water. 'l hereby a precipitate is separatiiid. which isinsoluble in allialies. It is liltered and washed with water.

The new compound. being probably the l methox 'naphthaleneflwarboxyamideof the formula:

crystallizes from water or dilute alcohol as long Colorless needles.melting at lhtl lfii' By saponil'ying the new compound with alkalineacting agents. for instance by heat-- ing it with a dilute caustic scdli solution. preferably with aodition of alcohoh until the evolution ofammonia eases, it is converted into the corresponding LmethoxynaplithaIene-Q-earbOXylie acid, which forms. when recrystallized from dilutealcohol bright needles, melting at 127, as described in literature (seeHiibner, Monatshet'te fur Chemie, vol. 15. pagei'35).

\Vhen using other aliphatic alcohols for the process the correspondingalkoxyderivatires are formed. The same reaction takes place when usingbenzylalcohol or also an aromatic phenol. lVith polyvalent alcohols suchas glycol the corresponding derivatives are formed.

Ewample 3.

1 part of the sodium salt of l-cyannaphtbalenel-sulphonie acid is addedat about 95 to a mixture of 4 parts of caustic potash and (3 parts ofmethylie alcohol. Then the mixture is heated under reflux for some hoursuntil a test as described in example 1 shows. that the formation of acompound, insoluble in dilute solutions of alkali carbonates, isfinished. After cooling down the mass is dilutxd with water and theseparated 4-1nethoxy-l-naphthamide of the formula:

UONII:

is isolated by filtration. It has the properties described in literature(cf. Gattermann, lliebie's Annaleu. vol. 244-. page T3, who prepared itin a complicated manner. unlit for technical purposes by reacting withureachloride and aluminiumchloride on wnaplu tholether).

\Vhen recrystallized from dilute alcohol it is obtained as colorlesscrystals, melting at 237". It is insoluble in cold alkalies, when heatedwith caustic alkaline solutions it is converted into the eorres'iomling' earboxylie acid.

hen in this process the temperature. of reaction is increased to about120 (by partly distilling oil the alcohol), evolution of ammonia begins:after heating the mass for some hours at this temperature until a test.when acidilieil. shows that the formation of a compound. easily solublein dilute solutions of alkali carbonates. is finished. the formed4-methoxy-l-naphthoic acid of the forn'uda:

eoou

ociu

separates by diluting the mas with water and :1cidil' \'in;: it. It iseasily soluble in all alies and melts 2115239". when recr\' tallimalfrom dilute alcohol (cf. lattermaim. l. e.). It may also he obtainedwhen ubjecting the 1-cyannaphthalene-4-sulphonic acid (see example 3 ofthe parent application) to the same process.

E wample .4.

If instead of methylic-alcohol ethylic alcohol is used and the processis otherwise carried out as described in the foregoing example, the-ethoxy-l-naphthau1ide and the 4-ethoxy-1-naphthoic-acid are obtained,having the properties, described in the literature (cf. Gattermann, l.c.). The -l-ethox vl-naphthamide crystallizes from dilute alcohol ascolorless needles, melting at 24 i. It is insoluble in cold alkalies,when heated with a caustic alkaline solution the corresponding acid isformed. This 4-ethoxy-1- naphthoic-acid crystallizes from dilute alcoholas colorless needles, melting at 214. It is easily soluble in alkalies.

Emample 5.

Vt hen using n-butylic alcohol instead of methylic alcohol and carryingout the reaction otherwise as described in the foregoing examples, atfirst the l-n-butyloxydnaphthamide of the formula:

oomn

OCHzCHzCII CHa is obtained. The new compound crystallizes from spirit insilver shining needles, melting at 250.

By increasing the temperature of the reaction the corresponding4-n-butyloxy-lnaphthoic acid of the formula:

coon

GHzCHzCUzC Ila is obtained, being also a new compound, crystallizingfrom spirit as colorless needles and melting at 208.

In an analogous manner allryloxy-compounds of higher fatty alcohols maybe produced.

Among the products of conversion, derived from orthoand para-cyannaphthalene-sulphonic acids, herein described, the hydroxynaphthoic-acidsobtainable accord ing to the aforesaid reaction with an excellent yieldand in a pure state are already known in the literature, Whereas thehydroxycyannaphthalone-compounds obtainable as intermediates by thisreaction, are new bodies. The alkoxynaphthamides andalkoXynaphthoic-acids are new compounds with exception of the following,which have been prepared in a complicated manner, un-

fit for technical purposes, as stated above: (1)2-methoxy-1-naphthamidc, (Licbigs Annalen, vol. 244, page2-etlioxy-l-naphthannde, (l. 0., page (3) 4-melhoxy-l-naphthamide, (l.c., page (4) 4-cthoxy-1-naphlhamide, (l. 0., page i5)Q-melhoxy-lmaplithoic acid (Bulletin 3, vol. 17, page 311) (6)Q-ethoxy-1-naphthoic acid, (Comptes rendus, vol. 136, page 618) (7)1-methoxy-Q-naphthoic acid (.\[on1tshefte fiir ClWIHiC, vol. 15, page735) (8) l-niethoxy-l-naphthoic acid, (Liebigs Annalen, vol. 244, page73) (9) Lethoxy-l-naphthoic acid, (I. c., page. 73).

This application contains subject matter in common with our co-pendingapplication Ser. No. 232.467, tiled November 10, 1927.

\Ve claim:

1. A new process for converting cyannaphthalene sulphonic acids of thefollowing general formula:

Cm a

soni, in which formula the Xs mean hydrogen atoms, of which one or moremay be replaced by a monovalent substituent, and the cyanogen and atleast one sulphogroup stand to each other in para-position, intoproducts of conversion of the probable formula:

CmXo

ooou, in which formula the alkoxygroup stands in paralposition to thecarboxylic group and the Xs mean hydrogen atoms, of which one or moremay be replaced by a monovalent substituent, which process comprisestreating para-cyannaphthalene sulphonic acids at temperatures from about100 to 150 C. with a caustic alkali in presence of an alcohol until atest, when acidified, shows that the product obtained is totally solublein dilute solutions of alkali carbonates.

2. A new process for converting cyannaphthalene sulphonic acids of thefollowing general formula: (w

CmXa

soul,

in which formula the Xs mean hydrogen atoms, of which one or more may bereplaced by a monovalent suhstituent, and the cyanoother in orthoorpara-position, into prodgcn and at least one sulphogronp stand to eachnets of conversion of the general formula:

CruXu coon,

in which formula the alkoxygroup stands in orthoor para-position to thecarboxylicgroup, and the Xs mean hydrogen atoms, of which one or moremay be replaced by a nionoralcnt substituent. which process comprisestreating cyannaphthalene-sulphonicacids corresponding to the aforesaidformula at temperatures from about to 150 C. with a caustic alkali inpresence of an alcohol until a test, when acidified, shows that theproduct obtained is insoluble in dilute solutions of alkali carbonates,and treating the products thus obtained with saponit'ying agents, untila test when :uriditied, shows, that the product obtained is totallysoluble in dilute solutions of alkali carbonates.

3. A new process for converting" l-cyannaphthalene-tealphonic acid intoa product of conversion of the probable formula coon which processcomprises treating t y a test, when acidified shows, that the productobtained is totally soluble in dilute solutions of alkali carbonates.

4. As a new compound the 4-n-butyloxy-1- naphthoic acid of the probableformula:

COOU

C lIzC IHCIH S being when dry a colorless powder, crystallizing fromspirit as colorless needles, easily soluble in dilute solutions ofalkali carbonates, which compound is substantially identical with aproduct obtainable by treating the l-cyannaphthalene--sulphonic acid attemperatures from about to with a caustic alkali in presence ofn-butylalcohol, until a test, when acidified, shows, that the productobtained is totally soluble in dilute solutions of alkalicarbonates.

In testimony whereof, we aflix our signatures.

RICHARD HERZ. FRITZ SCHULTE. WERNER ZERWECK.

CERTIFICATE OF CORRECTION.

Patent No. 1,669. 297.

Granted May 8, 1928, to

RICHARD HERZ ET AL.

It is hereby certified that e above numbered patent requiring record ofthe case in the Patent Office.

rror appears in the printed specification of the 124 i correction asfollows: i

and 125, and insert instead "gen and at least one so other in orthoorpara-position, into prod-" should be read with this correction thereinPage 3, strike out linen lphogroup stand to each and that the saidLetters Patent that the same may conform to the Signed and sealed this5th day of June, A. D. 1928.

(Seal) M. J. Moore, Acting Commissioner of Patents.

[ill

orthoor para-position to the carboxylicgroup, and the Xs mean hydrogenatoms, of which one or more may be replaced by a nionoralcntsubstituent. which process comprises treatingcyannaphthalene-sulphonicacids corresponding to the aforesaid formula attemperatures from about to 150 C. with a caustic alkali in presence ofan alcohol until a test, when acidified, shows that the product obtainedis insoluble in dilute solutions of alkali carbonates, and treating theproducts thus obtained with saponit'ying agents, until a test when:uriditied, shows, that the product obtained is totally soluble indilute solutions of alkali carbonates.

3. A new process for converting" l-cyannaphthalene-tealphonic acid intoa product of conversion of the probable formula coon which processcomprises treating t y a test, when acidified shows, that the productobtained is totally soluble in dilute solutions of alkali carbonates.

4. As a new compound the 4-n-butyloxy-1- naphthoic acid of the probableformula:

COOU

C lIzC IHCIH S being when dry a colorless powder, crystallizing fromspirit as colorless needles, easily soluble in dilute solutions ofalkali carbonates, which compound is substantially identical with aproduct obtainable by treating the l-cyannaphthalene--sulphonic acid attemperatures from about to with a caustic alkali in presence ofn-butylalcohol, until a test, when acidified, shows, that the productobtained is totally soluble in dilute solutions of alkalicarbonates.

In testimony whereof, we aflix our signatures.

RICHARD HERZ. FRITZ SCHULTE. WERNER ZERWECK.

CERTIFICATE OF CORRECTION.

Patent No. 1,669. 297.

Granted May 8, 1928, to

RICHARD HERZ ET AL.

It is hereby certified that e above numbered patent requiring record ofthe case in the Patent Office.

rror appears in the printed specification of the 124 i correction asfollows: i

and 125, and insert instead "gen and at least one so other in orthoorpara-position, into prod-" should be read with this correction thereinPage 3, strike out linen lphogroup stand to each and that the saidLetters Patent that the same may conform to the Signed and sealed this5th day of June, A. D. 1928.

(Seal) M. J. Moore, Acting Commissioner of Patents.

[ill

